JPS6313939B2 - - Google Patents
Info
- Publication number
- JPS6313939B2 JPS6313939B2 JP55096264A JP9626480A JPS6313939B2 JP S6313939 B2 JPS6313939 B2 JP S6313939B2 JP 55096264 A JP55096264 A JP 55096264A JP 9626480 A JP9626480 A JP 9626480A JP S6313939 B2 JPS6313939 B2 JP S6313939B2
- Authority
- JP
- Japan
- Prior art keywords
- section
- reaction
- raw material
- reaction tube
- material slurry
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000006243 chemical reaction Methods 0.000 claims description 60
- 239000002002 slurry Substances 0.000 claims description 43
- 238000010438 heat treatment Methods 0.000 claims description 26
- 239000002994 raw material Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 229960004887 ferric hydroxide Drugs 0.000 claims description 13
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 13
- 238000011084 recovery Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims 3
- 238000011027 product recovery Methods 0.000 claims 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 239000000284 extract Substances 0.000 claims 1
- 229910052598 goethite Inorganic materials 0.000 description 36
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 36
- 239000002245 particle Substances 0.000 description 25
- 239000006247 magnetic powder Substances 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000005755 formation reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 3
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 3
- 239000006249 magnetic particle Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- -1 goethite Chemical compound 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Description
【発明の詳細な説明】
本発明は、含水酸化鉄の製造方法及び装置に関
するものであり、特には磁気記録用材料として汎
用されている鉄系の針状磁性粉末を製造するに当
つての出発物質となる含水酸化鉄を工業的規模で
効率的に製造するのに特に適した連続的製造方法
及び装置に関係する。Detailed Description of the Invention The present invention relates to a method and apparatus for producing hydrated iron oxide, and in particular to a starting point for producing iron-based acicular magnetic powder, which is widely used as a magnetic recording material. The present invention relates to a continuous production method and apparatus particularly suitable for efficiently producing hydrated iron oxide as a substance on an industrial scale.
近年、含水酸化鉄粉末の用途は多方面に広が
り、顔料はもとより、フエライト製造の原料とし
てあるいは磁気記録用の磁性粉末製造の原料とし
てその使用量が増大している。 In recent years, the use of hydrated iron oxide powder has expanded to a wide range of fields, and its usage has increased not only as a pigment but also as a raw material for producing ferrite or as a raw material for producing magnetic powder for magnetic recording.
含水酸化鉄粉末が磁気記録用磁性粉末製造のた
めの出発物質として使用される場合、含水酸化鉄
粉末の形状が磁性粉末に受継がれるので、磁気記
録用途に適した磁性粉末の形状に相応する形態を
有する含水酸化鉄粉末を製造する必要がある。即
ち、磁気記録用磁性粉末の特性のうちで重要とさ
れているものに、粒子の保磁力、塗料化した時の
粒子の分散性、テープ中での粒子の配向性等があ
り、これらの良否が最終的な磁気テープの特性を
大きく左右する。粒子のこれら特性に直接関与す
るのは粒子の形状である。例えば、通常の記録材
料のように、形状異方性によつて保磁力を得てい
る場合、粒子の針状性が向上すればする程、その
保磁力は増大する。また、針状粒子であつてもそ
の枝分れや彎曲が少くなればなる程、塗料化に際
しての分散性は向上しそしてテープ化時の配向処
理に際しての立体障害的な要素も無くなるために
テープ中での配向性も向上し、その結果テープの
磁気記録特性が向上する。従つて、磁気記録用磁
性粉末を製造する場合、針状性が良好で且つ枝分
れや彎曲の少ない磁性粒子を使用することが重要
である。磁気記録用磁性粉末を工業的に生産する
には、針状形の粒子として成長しやすい含水酸化
第二鉄（主としてゲータイト、αFeOOH）を先
ず作成し、これを出発物質として加熱、脱水、還
元を行つて磁性金属鉄粒子とするか、還元を途中
で止めてFe3O4粒子とするか、或いは更にこれを
酸化してγFe2O3粒子とする方法が現在のところ
広く採用されている。この方法で得られる磁性粒
子はすべて、出発物質たる含水酸化鉄（以下ゲー
タイトによつて代表する）の形状を受継ぐ形骸粒
子となるから、前述した通り、秀れた磁気記録用
磁性粒子を入手するには出発物質たるゲータイト
粒子の形状の制御が必要とされるのである。 When hydrous iron oxide powder is used as a starting material for producing magnetic powder for magnetic recording, the shape of the hydrous iron oxide powder is inherited by the magnetic powder, so that it corresponds to the shape of the magnetic powder suitable for magnetic recording applications. It is necessary to produce hydrated iron oxide powder having a specific morphology. In other words, the important properties of magnetic powder for magnetic recording include the coercive force of the particles, the dispersibility of the particles when made into a paint, and the orientation of the particles in the tape. greatly influences the characteristics of the final magnetic tape. Directly responsible for these properties of the particles is the shape of the particles. For example, when the coercive force is obtained through shape anisotropy, as in normal recording materials, the coercive force increases as the acicularity of the particles improves. In addition, even if the particles are acicular, the less branching and curvature they have, the better their dispersibility will be when made into a paint, and the steric hindrance factors will be eliminated during the orientation process when making a tape. The orientation within the tape is also improved, and as a result, the magnetic recording properties of the tape are improved. Therefore, when producing magnetic powder for magnetic recording, it is important to use magnetic particles that have good acicularity and less branching and curvature. To industrially produce magnetic powder for magnetic recording, hydrated ferric oxide (mainly goethite, αFeOOH), which easily grows as needle-shaped particles, is first created, and this is used as a starting material by heating, dehydration, and reduction. At present, methods are widely adopted, such as oxidizing the particles to form magnetic metal iron particles, stopping the reduction midway through to form Fe 3 O 4 particles, or further oxidizing the particles to form γFe 2 O 3 particles. All the magnetic particles obtained by this method are skeleton particles that inherit the shape of the starting material, hydrated iron oxide (hereinafter referred to as goethite), so as mentioned above, excellent magnetic particles for magnetic recording can be obtained. In order to do this, it is necessary to control the shape of the goethite particles that are the starting material.
以上の理由で、磁気記録用磁性粉末の製造のた
めには、適正な形態特性を有するゲータイトを効
率的にそして経済的に製造しうる方法の確立が先
ず必要であり、様々の試行が行われつつある。 For the above reasons, in order to manufacture magnetic powder for magnetic recording, it is first necessary to establish a method for efficiently and economically manufacturing goethite with appropriate morphological characteristics, and various trials have been carried out. It's coming.
さて、ゲータイトの製造方法として従来よりも
つとも広く検討されまた工業的にも広く採用され
ている方法は、第一鉄塩にアルカリを加えて生じ
る水酸化第一鉄沈殿物を酸性、中性あるいはアル
カリ性溶液中で酸化するものである。液中の鉄イ
オンの濃度、液のPH、温度等を変え更に酸化反応
の速度を制御することにより種々の形状のゲータ
イト粒子が得られている。しかし、この方法で
は、第一鉄イオンの緩慢な酸化反応によつてゲー
タイト結晶粒子を析出させるため長時間にわたる
反応を必要とし、このため反応条件を一定に保つ
て均一な酸化反応状態を維持することが困難であ
り、その結果生成する粒子の寸法分布が広がりや
すい。更に、この方法の場合、水酸化第一鉄から
ゲータイトに変換する過程で中間生成物として六
角板状のグリーンラスト（green rust）が一旦生
成されそしてその表面でグリーンラストの溶解と
第一鉄イオンの酸化そしてゲータイトの析出と云
つたエピタキシヤル反応が生起するとされてお
り、このため互いに約120℃の角をなす枝分れの
多いゲータイト粒子が生成しやすいことも重大な
欠点である。 Now, the method for manufacturing goethite that has been widely studied and widely adopted industrially is to add an alkali to ferrous salt and then add the ferrous hydroxide precipitate to acidic, neutral or alkaline solution. It oxidizes in solution. Goethite particles of various shapes are obtained by changing the concentration of iron ions in the liquid, the pH of the liquid, the temperature, etc., and controlling the rate of the oxidation reaction. However, this method requires a long reaction time to precipitate goethite crystal particles through a slow oxidation reaction of ferrous ions, so it is necessary to keep the reaction conditions constant to maintain a uniform oxidation reaction state. As a result, the size distribution of the particles produced tends to be wide. Furthermore, in the case of this method, hexagonal plate-shaped green rust is once generated as an intermediate product in the process of converting ferrous hydroxide to goethite, and on its surface, the green rust dissolves and ferrous ions are generated. It is said that epitaxial reactions such as oxidation of oxidation and precipitation of goethite occur, and this tends to produce highly branched goethite particles that form angles of about 120°C with each other, which is also a serious drawback.
また別のゲータイトの製造方法として、塩化第
二鉄を代表とする第二鉄塩を原料とする方法があ
る。この方法は、第二鉄塩に強アルカリを加える
ことにより水酸化第二鉄の沈殿を生成し、これを
水熱処理によつてゲータイトに変換することを基
本とするものであり、第一鉄塩を原料とする場合
に較べ酸化という反応を必要としないため上述し
た欠点を排除することができ、粒度分布の揃つた
枝分れのないゲータイト粒子を製造することがで
きる点で有益である。しかし、この方法は、工業
的な製造法としての観点から見た場合、反応を
100℃以上で行うための圧力容器を必要とし、そ
のため操業の連続性、効率性、容易性、信頼性等
が確保されないことが大きな欠点となつている。 Another method for producing goethite is a method using ferric salt, typified by ferric chloride, as a raw material. This method is based on adding a strong alkali to ferric salt to form a precipitate of ferric hydroxide, which is then converted to goethite through hydrothermal treatment. It is advantageous in that it does not require an oxidation reaction compared to when it is used as a raw material, so the above-mentioned drawbacks can be eliminated, and unbranched goethite particles with a uniform particle size distribution can be produced. However, from the perspective of an industrial production method, this method
A major drawback is that it requires a pressure vessel to operate at temperatures above 100°C, and as a result, continuity, efficiency, ease, reliability, etc. of operation cannot be ensured.
上記欠点に鑑み、本発明者は、オートクレーブ
を用いた多くの実験を重ねた結果、原料スラリー
を加圧状態で連続的に且つきわめて効率的に短時
間に反応を行わせる装置を開発するのに成攻し、
これに基いて水酸化第二鉄沈殿の水熱反応による
ゲータイト化の工業的連続製造法を確立した。 In view of the above-mentioned drawbacks, the inventor has conducted many experiments using autoclaves, and as a result, the inventor has developed an apparatus that allows raw material slurry to undergo a reaction under pressure continuously and extremely efficiently in a short period of time. Successfully attacked,
Based on this, an industrial continuous production method for goethite formation by hydrothermal reaction of ferric hydroxide precipitation was established.
本方法は、加熱装置内に屈曲して置かれた反応
管を通して加圧された原料スラリを流送し、反応
管内部を通しての移動中ゲータイト化反応を完結
せしめそしてそれを反応管から取出すことを基本
とする。反応管を通しての流送中、原料スラリは
ゲータイト化反応を完了するに充分の圧力及び温
度下に所要時間置かれる。原料スラリの種類及び
目的とする生成物品質水準に応じて、反応管を通
しての移送量、反応管の径及び長さ、加熱温度、
加熱態様等を適宜調整することにより、原料スラ
リは自在に品質管理されうる。 The method involves flowing a pressurized feed slurry through a reaction tube bent into a heating device, allowing the goethitization reaction to complete during the passage through the interior of the reaction tube, and removing it from the reaction tube. Basic. During flow through the reaction tube, the feed slurry is subjected to sufficient pressure and temperature for a period of time to complete the goethitization reaction. Depending on the type of raw material slurry and the desired product quality level, the amount transferred through the reaction tube, the diameter and length of the reaction tube, the heating temperature,
By appropriately adjusting the heating mode, etc., the quality of the raw material slurry can be freely controlled.
以下、図面を参照しつつ本発明について具体的
に説明する。 The present invention will be specifically described below with reference to the drawings.
本発明において、原料として利用されるスラリ
は、アルカリ性の水酸化第二鉄沈殿生成直後のも
の、生成後一定時間熟成させたもの、あるいはこ
れらの混合物、更には第一鉄塩の酸化によつて調
製した水酸化第二鉄沈殿物である。これら沈殿物
は更に、ゲータイト化反応を促進するための反応
促進剤や生成物の品質改良のための添加剤を含有
しうることはいうまでもない。例えば、生成ゲー
タイトを少量含ませることもできるし、また鉄に
対して例えば８％程度までのCo，Ni，Zn，Al及
びMnを含ませることもできる。これらを包括し
て以下原料スラリと呼ぶ。 In the present invention, the slurry used as a raw material may be one immediately after the alkaline ferric hydroxide precipitate is formed, one that has been aged for a certain period of time after the formation, or a mixture thereof, or a slurry prepared by oxidation of ferrous salt. This is the prepared ferric hydroxide precipitate. It goes without saying that these precipitates may further contain reaction accelerators for accelerating the goethite formation reaction and additives for improving the quality of the product. For example, a small amount of generated goethite can be included, and Co, Ni, Zn, Al, and Mn can also be included, for example, up to about 8% relative to iron. These are collectively referred to as the raw material slurry hereinafter.
第１図を参照すると、原料スラリは原料タンク
T1からポンプP1を通して反応帯域に送り出され
る。ポンプP1は反応圧力以上の送入圧力を創出
しうるポンプでありまた逆方向へのスラリの流れ
を防止する働きも兼ねたものである。ポンプP1
によつて所定圧まで高められた一定流量の原料ス
ラリは、弁V1を介して加熱装置Ｈ内に屈曲して
収納される反応管Ｂに流れ込む。 Referring to Figure 1, the raw material slurry is stored in the raw material tank.
From T 1 it is pumped into the reaction zone through pump P 1 . Pump P1 is a pump capable of creating a feed pressure higher than the reaction pressure, and also serves to prevent slurry from flowing in the opposite direction. Pump P 1
A constant flow rate of the raw material slurry, which has been raised to a predetermined pressure by the above, flows into the reaction tube B, which is bent and housed in the heating device H, via the valve V1 .
加熱装置Ｈは、反応管を直接加熱する電気ヒー
タ、熱媒の入つた恒温槽、熱交換器等任意の形態
をとりうる。制御温度は反応条件あるいはスラリ
条件によつて異なるが、一般に60〜200℃の範囲
である。加熱装置内で反応管の上流から下流へと
加熱度を変更するため、加熱装置内を幾つかのゾ
ーンに分画することもできる。例えば第１図に点
線で示すように加熱装置内の反応管最終行路部分
に対応するゾーンH1をやや高い温度に保持して
反応の完結を保証するようになしうる。 The heating device H can take any form such as an electric heater that directly heats the reaction tube, a constant temperature bath containing a heating medium, or a heat exchanger. The controlled temperature varies depending on the reaction conditions or slurry conditions, but is generally in the range of 60 to 200°C. In order to change the heating degree from upstream to downstream of the reaction tube within the heating device, the inside of the heating device can also be divided into several zones. For example, as indicated by the dotted line in FIG. 1, zone H1 in the heating device, which corresponds to the final passage of the reaction tube, may be maintained at a slightly higher temperature to ensure completion of the reaction.
反応管Ｂは、10〜20Kg／cm2の圧力に耐え、そし
て耐アルカリ性及び耐熱性を具備するものなら任
意の材料製となしえ、例えばステンレス鋼やチタ
ン、ニツケルあるいはその合金、更には高圧用テ
フロン製チユーブとされる。反応管Ｂは、所要の
行路長を得るよう加熱装置Ｈ内で屈曲されてい
る。 Reaction tube B can be made of any material as long as it can withstand a pressure of 10 to 20 kg/cm 2 and has alkali resistance and heat resistance, such as stainless steel, titanium, nickel or its alloys, and even high-pressure materials. It is believed to be a Teflon tube. The reaction tube B is bent within the heating device H to obtain the required path length.
加熱装置Ｈを所定温度へ昇温後、ポプP1によ
り原料スラリを反応管Ｂに送入する前に、反応管
系を反応圧力まであらかじめ昇圧することが反応
の開始に先立つて必要である。これにより反応管
内部での水蒸発によるスラリの焼きつきを防止す
ることができる。これは、コンプレツサP3によ
り反応管系に所定圧の空気を送入することにより
達成される。 After heating the heating device H to a predetermined temperature and before feeding the raw material slurry into the reaction tube B using the pop P1 , it is necessary to increase the pressure of the reaction tube system to the reaction pressure in advance before starting the reaction. This can prevent the slurry from sticking due to water evaporation inside the reaction tube. This is achieved by introducing air at a predetermined pressure into the reaction tube system by compressor P3 .
反応管Ｂにおいて充分に加熱され、ゲータイト
化したスラリは、ポンプP2を介して回収タンク
T2に送出される。ポンプP2と回収タンクT2との
間には弁V8が組込まれている。ポンプP2はポン
プP1とは逆の機能を有し、反応圧力以上の背圧
に耐え、常にP1の送入量と同量の生成ゲータイ
トスラリを排出しうるポンプである。P1とP2と
は同期されている。 The slurry that has been sufficiently heated and turned into goethite in the reaction tube B is sent to the recovery tank via pump P2 .
Sent on T 2 . A valve V 8 is installed between the pump P 2 and the recovery tank T 2 . Pump P 2 has the opposite function to pump P 1 , is a pump that can withstand back pressure higher than the reaction pressure, and can always discharge the produced goethite slurry in an amount equal to the amount fed in by P 1 . P 1 and P 2 are synchronized.
反応圧力は、反応温度での水の蒸気圧以上であ
れば良く、本装置の場合、150℃における水の蒸
気圧（約５Kg／cm2）を考慮して上限は10Kg／cm2そ
して下限は１Kg／cm2とされる。 The reaction pressure only needs to be higher than the vapor pressure of water at the reaction temperature; in the case of this device, the upper limit is 10 Kg/cm 2 and the lower limit is 10 Kg/cm 2 considering the vapor pressure of water at 150°C (approximately 5 Kg/cm 2 ). It is assumed to be 1Kg/ cm2 .
系内に圧力異常が発生した場合、それに対処す
るために、反応管からポンプP2の上流の地点で
分岐管が設けられ、そこに安全弁Ｓが設けられて
いる。更には、圧力計A2がその設定上限値を検
知する時、弁V5及びV6或いはV9を自動的に開き
そしてポンプP1及びP2を停止するように為され
ている。 In order to cope with the occurrence of pressure abnormality in the system, a branch pipe is provided at a point upstream of the pump P2 from the reaction tube, and a safety valve S is provided there. Furthermore, when the pressure gauge A 2 detects its upper limit value, the valves V 5 and V 6 or V 9 are automatically opened and the pumps P 1 and P 2 are stopped.
圧力計A1は送入圧力を検知しそして弁V3はサ
ンプリング用のものである。これらは所定の条件
にない原料スラリが送入された場合ポンプP1を
停止したりあるいは原料スラリの条件に応じて加
熱装置の温度を調節するためのものである。 Pressure gauge A 1 detects the inlet pressure and valve V 3 is for sampling. These are used to stop the pump P1 when a raw material slurry that does not meet predetermined conditions is fed, or to adjust the temperature of the heating device according to the raw material slurry conditions.
反応管の途中にもサンプリング手段を設け、そ
してその結果に応じてそれより下流側での反応管
温度の調節をなすこともできる。 It is also possible to provide a sampling means in the middle of the reaction tube, and adjust the temperature of the reaction tube downstream from it according to the results.
弁V3及びV7は洗浄水導入用であり、操業中配
管系あるいはタンクの洗浄が必要になつた適宜の
時点で洗浄操作が実施される。弁11は大気開放用
の弁である。 Valves V 3 and V 7 are for introducing cleaning water, and cleaning operations are carried out at appropriate times during operation when cleaning of the piping system or tank becomes necessary. Valve 11 is a valve for opening to the atmosphere.
ゲータイト化反応を完了しそして所定の品質水
準に達したゲータイト生成物はポンプP2から回
収タンクT2に送出された後、弁V10を通して用途
に応じて所定の処理工程に供される。後に実施例
に示すように、完全にゲータイト化を完了しそし
て粒度分布にすぐれたゲータイト生成物が入手さ
れうる。 The goethite product that has completed the goethiteization reaction and has reached a predetermined quality level is sent from the pump P 2 to the recovery tank T 2 and then subjected to a predetermined processing step depending on the application through the valve V 10 . As shown in the examples below, a goethite product which is completely goethitized and has an excellent particle size distribution can be obtained.
次に、第２図を参照すると、本発明方法を実施
する別の具体例が示されている。この場合、反応
管からのゲータイト生成物の取出し系が第１図と
異る。第２図の反応管より上流側の設備は第１図
と同じであるから、説明は省略する。第２図の場
合、生成ゲータイトスラリは、反応管Ｂと同圧の
バツフアタンクT3にひとまず導入されそして後
そこから回収タンクT4に送出される。バツフア
タンクT3における圧力累積を避けるために、P1
による送出圧力分は常に逃し弁Ｓを介して大気に
解放される。反応の継続に伴い、反応管Ｂから弁
V14を介してバツフアタンクT3に送出されそして
そこに溜まる生成ゲータイトスラリの水準はレベ
ル計Ｌによつて検知される。レベル計Ｌが最高許
容液面水準を検知すると、自動的にポンプP1が
停止しそして弁V14を閉じそして弁V16が開かれ
るようになつている。弁V16が開くことにより、
バツフアタンクT3内の生成ゲータイトスラリは
余圧によつてそのまま回収タンクT4に移送され
る。バツフアタンク系内の圧力が次第に下がり、
それが圧力計A4の設定下限値を越えると弁15が自
動的に開き、コンプレツサP4を通して空気がバ
ツフアタンクT3に圧入されるようになつている。
こうして、生成ゲータイトスラリはタンクT3か
ら連続的に放出されていきそしてその液面がレベ
ル計Ｌの最低許容液面水準に達すると、弁V16は
自動的に閉となり更に続いてのコンプレツサP4
からの空気の圧入によつて圧力が圧力計Ａ−４の
設定上限値を越えた時点で弁V15が閉じられ、そ
して弁V14が開かれると共にポンプP1が作動さ
れ、反応が再開される。バツフアタンクから弁16
を介して放出された生成ゲータイトスラリは回収
タンクT4に移されそこから弁18を通して爾後処理
に供される。 Referring now to FIG. 2, another embodiment of implementing the method of the present invention is shown. In this case, the system for removing the goethite product from the reaction tube is different from that in FIG. The equipment upstream of the reaction tube in FIG. 2 is the same as in FIG. 1, so a description thereof will be omitted. In the case of FIG. 2, the produced goethite slurry is first introduced into a buffer tank T3 having the same pressure as the reaction tube B, and then sent from there to a recovery tank T4 . To avoid pressure accumulation in the buffer tank T 3 , P 1
The delivery pressure is always released to the atmosphere via the relief valve S. As the reaction continues, the valve is removed from reaction tube B.
The level of the produced goethite slurry, which is delivered via V 14 to the buffer tank T 3 and accumulates there, is detected by a level meter L. When the level meter L detects the highest permissible liquid level, the pump P 1 is automatically stopped, the valve V 14 is closed and the valve V 16 is opened. By opening valve V 16 ,
The generated goethite slurry in the buffer tank T 3 is directly transferred to the recovery tank T 4 by the excess pressure. The pressure inside the buffer tank system gradually decreases,
When it exceeds the lower limit set by the pressure gauge A4 , the valve 15 is automatically opened and air is forced into the buffer tank T3 through the compressor P4 .
In this way, the generated goethite slurry is continuously discharged from the tank T3 , and when the liquid level reaches the minimum permissible liquid level level of the level meter L, the valve V16 is automatically closed and the subsequent compressor P is discharged. Four
When the pressure exceeds the upper limit set by the pressure gauge A-4 due to the air being injected from the pump, the valve V15 is closed, and the valve V14 is opened and the pump P1 is activated to restart the reaction. Ru. Valve 16 from the buffer tank
The produced goethite slurry discharged via is transferred to a recovery tank T 4 from where it is passed through valve 18 for subsequent treatment.
バツフアタンクT3には生成ゲータイト取出し
用予備バルブV17及び圧力均等管Ｅが装備されて
いる。第１図と同じく、圧力計A3、大気開放用
弁12、洗浄水流入弁V13等の設備も然るべく設け
られている。 The buffer tank T3 is equipped with a spare valve V17 for taking out the generated goethite and a pressure equalization pipe E. As in FIG. 1, equipment such as a pressure gauge A 3 , an atmosphere release valve 12 and a wash water inlet valve V 13 are also provided as appropriate.
以上の第２図の構成は第１図のポンプP2の使
用を排除し、生成ゲータイトスラリの反応管から
の取出し操作を円滑化する。 The above configuration of FIG. 2 eliminates the use of the pump P 2 of FIG. 1 and facilitates the operation of removing the produced goethite slurry from the reaction tube.
本発明により、水酸化第二鉄の加熱あるいは加
圧によるゲータイトへの変換を連続的に行うこと
が可能とされたわけであるが、その特徴を列記す
れば次のようになる：
(1) 操業の連続性が実現され、工業化を可能なら
しめたこと。 The present invention has made it possible to continuously convert ferric hydroxide into goethite by heating or pressurizing, and its characteristics are listed as follows: (1) Operation continuity was realized, making industrialization possible.
(2) 圧力容器の使用を排除したことにより、設備
費を安くしまた操業を容易化したこと。(2) By eliminating the use of pressure vessels, equipment costs are reduced and operations are made easier.
(3) 加熱効率が向上し、従来の方式に較べて急速
加熱が可能であり、このため粒度の揃つたゲー
タイトが得られること。(3) The heating efficiency is improved, and rapid heating is possible compared to conventional methods, which allows goethite with uniform particle size to be obtained.
(4) 加熱作用の変更が容易に実施しうるから生成
物の品質の一様化が実現しうること（反応管の
径及び長さ、加熱温度、ポンプ送り量、段階的
加熱等による）。(4) Uniform product quality can be achieved because the heating action can be easily changed (depending on the diameter and length of the reaction tube, heating temperature, pumping rate, stepwise heating, etc.).
(5) 反応開始前に系内を予圧しておくことにより
反応管内のスラリ焼付きを防止しうること。(5) By prepressurizing the system before starting the reaction, it is possible to prevent slurry from burning inside the reaction tube.
(6) ゲータイト化反応は反応管を一回通過するだ
けで完了するので、大量生産の場合でも設備が
小さくてすむこと。(6) Since the goethite formation reaction is completed in just one pass through the reaction tube, the equipment can be small even for mass production.
(7) 圧力異常に対する処置も自動化でき、生産を
殆んど無人化しうること。(7) Measures against pressure abnormalities can also be automated, making production almost unmanned.
以下、本発明の実施例を示すが、ここで使用す
る原料スラリとしては、0.09MのZnCl2を含む3M
のFeCl3溶液１中に2.7MのNaOH4.5を毎分
50c.c.の割合で滴下し、得られた水酸化第二鉄沈殿
物をそのまま24時間室温で放置することにより熟
成したものを使用した。 Examples of the present invention are shown below, and the raw material slurry used here is 3M containing 0.09M ZnCl2 .
2.7M NaOH4.5 in FeCl3 solution 1 min.
It was added dropwise at a rate of 50 c.c., and the obtained ferric hydroxide precipitate was left as it was at room temperature for 24 hours to mature.
実施例 １
上記熟成処理ずみのZn2+3原子％を含むPH13.5
の水酸化第二鉄沈殿物スラリを毎時10で第２図
に示したのと同等の装置を用いて反応させた。系
内の圧力は７Kg／cm2としそして加熱装置の温度は
恒温槽を用いて150℃に維持した。反応管として
は容積10のテフロンチユーブを使用した。連続
的に得られたスラリは従来のバツチ式で得られた
よりもより粒度分布に秀れたゲータイトであつ
た。Example 1 PH13.5 containing Zn 2+ 3 atomic % after the above aging treatment
of the ferric hydroxide precipitate slurry was reacted at 10 per hour using an apparatus similar to that shown in FIG. The pressure in the system was 7 Kg/cm 2 and the temperature of the heating device was maintained at 150° C. using a constant temperature bath. A Teflon tube with a volume of 10 was used as the reaction tube. The slurry obtained continuously was goethite with a better particle size distribution than that obtained by the conventional batch method.
実施例 ２
実施例１と同様の条件で、スラリの送り速度の
みを毎時20と変えて操作を行つた。得られるス
ラリはすべてゲータイトであつた。尚、この時反
応管を出たところの位置で測定したスラリの温度
は110℃であつた。Example 2 An operation was carried out under the same conditions as in Example 1, except that the slurry feed rate was changed to 20 per hour. The resulting slurry was all goethite. At this time, the temperature of the slurry measured at the position where it exited the reaction tube was 110°C.
実施例 ３
実施例１で使用した熟成処理ずみの水酸化第二
鉄スラリに対して倍量の新たに調製した水酸化第
二鉄スラリを混合し、これを毎時10の送り速度
でもつて反応させた。圧力は４Kg／cm2そして温度
は130℃とした。得られたスラリはすべてゲータ
イトであつた。Example 3 Double the amount of freshly prepared ferric hydroxide slurry was mixed with the aged ferric hydroxide slurry used in Example 1, and the mixture was allowed to react at a feed rate of 10 per hour. Ta. The pressure was 4 Kg/cm 2 and the temperature was 130°C. The resulting slurry was all goethite.
実施例 ４
ゲータイトに対し等量の鉄を含む水酸化第一鉄
沈殿を混合し、PH12とした後空気バブリングで酸
化することによつて生成したスラリを毎時10の
速度で連続合成した。加熱装置の温度は90℃とし
た。スラリの出口温度は60℃であつた。得られた
スラリはすべて粒度分布の良いゲータイトであつ
た。Example 4 A slurry produced by mixing ferrous hydroxide precipitate containing an equal amount of iron to goethite, adjusting the pH to 12, and oxidizing with air bubbling was continuously synthesized at a rate of 10 per hour. The temperature of the heating device was 90°C. The exit temperature of the slurry was 60°C. All of the obtained slurry was goethite with a good particle size distribution.
第１図及び第２図は、本発明方法を実施するに
好適な設備の概略フローシートである。
T1：原料タンク、P1：ポンプ、Ｈ：加熱装置、
Ｂ：反応管、Ｐ：ポンプ、T2：回収タンク、
T3：バツフアタンク、A1〜4：圧力計、Ｓ：安全
弁、Ｌ：レベル計。
1 and 2 are schematic flow sheets of equipment suitable for carrying out the method of the present invention. T1 : Raw material tank, P1 : Pump, H: Heating device,
B: Reaction tube, P: Pump, T2 : Recovery tank,
T3 : Buffer tank, A1-4 : Pressure gauge, S: Safety valve, L: Level gauge.
Claims (1)
で反応管を通して流送しつつ60〜200℃の温度に
加熱することを特徴とする含水酸化第二鉄の製造
方法。 ２ 水酸化第二鉄原料スラリが鉄に対して８％ま
でのCo，Ni，Zn，Al及びMnのうちから選択さ
れる少く共一種を含んでいる特許請求の範囲第１
項記載の方法。 ３ 水酸化第二鉄原料スラリが熟成処理ずみとさ
れている特許請求の範囲第１項記載の方法。 ４ アルカリ性水酸化第二鉄原料スラリを送入す
る原料送入部と、該送入部から流送された原料ス
ラリを加熱する反応部と、該反応部から生成含水
酸化第二鉄を取出す生成物回収部とを含み、前記
送入部が原料スラリを加圧して前記反応部に送入
するためのポンプを備え、前記反応部が加熱装置
及びそれと関連して設けられる反応管から構成さ
れ、そして前記回収部が高圧の反応生成物を大気
圧下で取出す手段を備えることを特徴とする含水
酸化第二鉄の製造装置。 ５ 生成物回収部が反応管の出口と回収タンクと
を繋ぐ管路内に配設されるポンプを含む特許請求
の範囲第４項記載の装置。 ６ 生成物回収部が反応管出口の下流に設けられ
る密閉バツフアタンクを含む特許請求の範囲第４
項記載の装置。 ７ バツフアタンクにレベル計と該レベル計から
の液面水準信号に応答して該バツフアタンクに外
部空気を圧入する手段を備える特許請求の範囲第
６項記載の装置。 ８ 反応部が反応管を予圧するためのコンプレツ
サを備える特許請求の範囲第４項記載の装置。[Claims] 1. A method for producing hydrous ferric oxide, which comprises heating an alkaline ferric hydroxide raw material slurry to a temperature of 60 to 200° C. while flowing it through a reaction tube under increased pressure. 2. Claim 1, wherein the ferric hydroxide raw material slurry contains up to 8% of Co, Ni, Zn, Al, and Mn based on iron.
The method described in section. 3. The method according to claim 1, wherein the ferric hydroxide raw material slurry is aged. 4 A raw material feed section that feeds the alkaline ferric hydroxide raw material slurry, a reaction section that heats the raw material slurry flowed from the feed section, and a generation section that extracts the hydrous ferric oxide produced from the reaction section. a material recovery section, the feeding section is equipped with a pump for pressurizing the raw material slurry and feeding it into the reaction section, and the reaction section is composed of a heating device and a reaction tube provided in connection therewith, An apparatus for producing hydrous ferric oxide, wherein the recovery section includes means for taking out the high-pressure reaction product under atmospheric pressure. 5. The device according to claim 4, wherein the product recovery section includes a pump disposed in a pipe line connecting the outlet of the reaction tube and the recovery tank. 6 Claim 4 in which the product recovery section includes a sealed buffer tank provided downstream of the outlet of the reaction tube
Apparatus described in section. 7. The apparatus according to claim 6, wherein the buffer tank includes a level meter and means for pressurizing external air into the buffer tank in response to a liquid level signal from the level meter. 8. The apparatus according to claim 4, wherein the reaction section includes a compressor for prepressurizing the reaction tube.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9626480A JPS5722121A (en) | 1980-07-16 | 1980-07-16 | Preparation of hydrous ferric hydroxide and apparatus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9626480A JPS5722121A (en) | 1980-07-16 | 1980-07-16 | Preparation of hydrous ferric hydroxide and apparatus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5722121A JPS5722121A (en) | 1982-02-05 |
| JPS6313939B2 true JPS6313939B2 (en) | 1988-03-28 |
Family
ID=14160305
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9626480A Granted JPS5722121A (en) | 1980-07-16 | 1980-07-16 | Preparation of hydrous ferric hydroxide and apparatus |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5722121A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60105001A (en) * | 1983-11-14 | 1985-06-10 | Mitsubishi Heavy Ind Ltd | Controller |
| JPS61111924A (en) * | 1984-11-06 | 1986-05-30 | Agency Of Ind Science & Technol | Production of acicular iron oxyhydroxide |
| JPH02263407A (en) * | 1989-04-04 | 1990-10-26 | Showa Denko Kk | Continuous manufacture of magnetic iron oxide powder for magnetic recording and device therefor |
-
1980
- 1980-07-16 JP JP9626480A patent/JPS5722121A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5722121A (en) | 1982-02-05 |
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